CN107188558B - A kind of alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density and preparation method thereof - Google Patents
A kind of alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004146 energy storage Methods 0.000 title claims abstract description 26
- 239000010949 copper Substances 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 18
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 238000005469 granulation Methods 0.000 claims abstract 2
- 230000003179 granulation Effects 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 4
- 229910003068 Ti(C4H9O)4 Inorganic materials 0.000 abstract description 2
- 239000002738 chelating agent Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003989 dielectric material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910002966 CaCu3Ti4O12 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 229910018576 CuAl2O4 Inorganic materials 0.000 description 1
- 229910002661 O–Ti–O Inorganic materials 0.000 description 1
- 229910002655 O−Ti−O Inorganic materials 0.000 description 1
- 229910020684 PbZr Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 229910003083 TiO6 Inorganic materials 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
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- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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Abstract
The invention discloses alumina doped copper titanate cadmium giant dielectric ceramic materials of a kind of high energy storage density and preparation method thereof, and the ceramic material is by CdCu3Ti4O12- x wt%Al2O3The material of expression forms, and it is with Cd (NO that wherein the value of x, which is 2~9,3)2·4H2O、Cu(NO3)2·3H2O、Ti(C4H9O)4For raw material, glacial acetic acid is chelating agent, first prepares precursor powder using sol-gel method, and precursor powder is calcined at a lower temperature, obtains the CdCu that can be mixed on a molecular scale and uniformity is preferable, activity is high3Ti4O12Then alumina powder is added in ceramic powder into ceramic powder, through ball milling, granulation, tabletting, dumping, sintering, alumina doped copper titanate cadmium giant dielectric ceramic material can be obtained.The preparation method of ceramic material of the present invention is simple, reaction temperature is lower, reproducible, high yield rate, and the dielectric properties of ceramic material are excellent, and energy storage density is up to 0.54~1.52mJ/cm3, it is with a wide range of applications.
Description
Technical field
The invention belongs to electron ceramic material technical fields, and in particular to arrive a kind of alumina doped metatitanic acid of high energy storage density
Copper cadmium giant dielectric ceramic material and preparation method thereof.
Background technique
With growing Information Technology Development, dielectric material has high dielectric constant, low-dielectric loss, high energy storage close
The property of degree is increasingly becoming capacitor element miniaturization, integrated, micromation key.Currently, the dielectric material being mostly used in the market
The mainly Ba of barium titanate seriesxSr1-xTiO3With the PbZr of lead titanates systemxTi1-xO3High dielectric constant material, but its dielectric constant
It has been far from satisfying electronic market demand.Both materials are affected by the external environment larger simultaneously, while lead-containing materials
It is unfavorable for environmental development, dielectric constant is not sufficiently stable.Subramanian in 2000 et al. takes the lead in reporting CaCu3Ti4O12
(CCTO) ceramic material has giant dielectric, not only has high dielectric constant, and temperature stability is also preferable, and
Also show strong nonlinear characteristic.But such material bias performance is poor, breakdown potential is forced down and dielectric loss is high (is greater than
10%), energy storage density is lower, limits its practical application in terms of energy-storage capacitor, is difficult to be widely used in capacitor, deposit
The electronic device of the high dielectric constant needed in the electronic markets such as reservoir.
Dielectric material is a kind of critical material of novel energy-storing developing material in 13 planning of country.Dielectric capacitor
The advantages of combining traditional capacitor and battery avoids the defect of electric chemical super capacitor, is that one kind has a extensive future
Solid state power supply.Compared to battery and electric chemical super capacitor, dielectric capacitor has high power density (higher than battery
5 orders of magnitude), momentary charge and charge and discharge process can be achieved be not related to electrochemical reaction, it is safe and reliable the advantages that, but it is stored up
Low 5 orders of magnitude of energy density ratio battery, the miniaturization for being unfavorable for energy-storage travelling wave tube.Therefore, high dielectric constant (> 10 is developed3), high storage
Can density dielectric material be there is an urgent need to.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of alumina doped metatitanic acid with compared with high energy storage density
Copper cadmium giant dielectric ceramic material, and a kind of preparation method is provided for it.
Ceramic material used by above-mentioned technical problem is solved by CdCu3Ti4O12- x wt%Al2O3The material group of expression
At wherein the value of x is 2~9, and preferably the value of x is 2~4.
The preparation method of the alumina doped copper titanate cadmium giant dielectric ceramic material of the present invention is made of following step:
1, according to CdCu3Ti4O12Stoichiometric ratio, by Cd (NO3)2·4H2O、Cu(NO3)2·3H2O is added to anhydrous
The in the mixed solvent of ethyl alcohol and deionized water is configured to solution A, by Ti (C4H9O)4It is added in dehydrated alcohol and is configured to solution B；
Solution A and solution B are mixed, and glacial acetic acid is added, the concentration of butyl titanate is 0.3~0.7mol/L, ice in gained mixed liquor
The volume fraction of acetic acid is 2.5%~10%, the volume fraction of deionized water is 5%~15%, is heated simultaneously at 30~75 DEG C
It stirs evenly, obtains colloidal sol, continue stirring until colloidal sol becomes gel, drying, obtains xerogel after gel is aged；It will be dry solidifying
After glue grinding, is calcined 8~10 hours at 600~700 DEG C, obtain CdCu3Ti4O12Ceramic powder.
2, to CdCu3Ti4O12The alumina powder of its quality 3%~12% is added in ceramic powder, through ball milling, dries, make
After grain, tabletting, dumping, it is sintered 10~15 hours at 970~1000 DEG C, obtains alumina doped copper titanate cadmium giant dielectric ceramics material
Material.
In above-mentioned steps 1, the concentration of butyl titanate is the volume fraction of 0.5mol/L, glacial acetic acid preferably in gained mixed liquor
Volume fraction for 5%, deionized water is 10%.
In above-mentioned steps 1, further preferably heats and stir evenly at 40~50 DEG C, obtain colloidal sol.
In above-mentioned steps 1, after more preferably grinding xerogel, calcined 10 hours at 650 DEG C.
In above-mentioned steps 2, it is sintered 15 hours preferably at 990 DEG C.
The present invention is with Cd (NO3)2·4H2O、Cu(NO3)2·3H2O、Ti(C4H9O)4For raw material, glacial acetic acid is chelating agent, first
Precursor powder is prepared using sol-gel method, and precursor powder is calcined at a lower temperature, obtains mixing on a molecular scale
Conjunction and the CdCu that uniformity is preferable, activity is high3Ti4O12Then alumina powder ball milling is added into ceramic powder, makes for ceramic powder
The alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density can be obtained in grain, tabletting, dumping, sintering.
The preparation method of ceramic material of the present invention is simple, reaction temperature is lower, reproducible, high yield rate, and ceramic material
The dielectric properties of material are excellent, and energy storage density may be up to 0.54~1.52mJ/cm3, can be used for preparing dynamic RAM electricity
The dielectric material of appearance is also expected to be used for high-voltage capacitor etc., is with a wide range of applications to store information.
Detailed description of the invention
Fig. 1 is the XRD diagram of the ceramic material of comparative example 1 and Examples 1 to 3 preparation.
Fig. 2 is the dielectric constant of the ceramic material of comparative example 1 and Examples 1 to 3 preparation with the variation relation of test frequency
Figure.
Fig. 3 is the raman scattering intensity of the ceramic material crystal grain of comparative example 1 and Examples 1 to 3 preparation with the variation of test wavelength
Relational graph.
Fig. 4 is nonlinear factor, work field strength and the energy storage density of the ceramics sample of comparative example 1 and Examples 1 to 3 preparation
With Al2O3The variation relation figure of doping.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1, according to CdCu3Ti4O12Stoichiometric ratio, by 3.1159g Cd (NO3)2·4H2O、7.3212g Cu
(NO3)2·3H2O is added to 10mL dehydrated alcohol and the in the mixed solvent of deionized water is configured to solution A, by 13.8mL Ti
(C4H9O)4It is added in 52.2mL dehydrated alcohol and is configured to solution B；Solution A and solution B are mixed, and 4mL glacial acetic acid is added,
The concentration of butyl titanate is 0.5mol/L in gained mixed liquor, the volume fraction of glacial acetic acid is 5.0%, the volume of deionized water point
Number be 10%, heat and stir evenly at 45 DEG C, obtain colloidal sol, continue stirring until colloidal sol become gel, gel is aged
It is 48 hours dry at 100 DEG C after 12 hours, obtain the loose shape xerogel of brown blue；After xerogel is ground, at 650 DEG C
Calcining 10 hours, obtains CdCu3Ti4O12Ceramic powder.
2, to CdCu3Ti4O12The alumina powder of its quality 3% is added in ceramic powder, using dehydrated alcohol as medium, uses
It behind agate ball ball milling 10 hours of 5~6mm, is dried at 80 DEG C, it is water-soluble that the polyvinyl alcohol that mass fraction is 5% is then added
Liquid, grinding are granulated, and after crossing 120 meshes, 11.5mm cylinder blank are pressed under 6MPa pressure with powder compressing machine, by cylinder
Shape blank is placed on zirconium oxide plate, was warming up to 500 DEG C with 380 minutes, is kept the temperature 2 hours, then with 2 DEG C/min of heating speed
Rate is warming up to 990 DEG C, Isothermal sinter 15 hours, cools to room temperature with the furnace, obtains the alumina doped copper titanate cadmium of high energy storage density
Giant dielectric ceramic material.
Embodiment 2
In the present embodiment, to CdCu3Ti4O12The alumina powder of its quality 6% is added in ceramic powder, other steps and reality
It is identical to apply example 1, obtains the alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density.
Embodiment 3
In the present embodiment, to CdCu3Ti4O12The alumina powder of its quality 9% is added in ceramic powder, other steps and reality
It is identical to apply example 1, obtains the alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density.
Comparative example 1
Alumina powder is not added, other steps are same as Example 1, obtain copper titanate cadmium giant dielectric ceramic material.
By ceramic material surfaces prepared by above-described embodiment 1~3 and comparative example 1 polishing, polishing, ultrasound, be wiped over it is clean,
Silver paste is respectively coated in its upper and lower surface, is placed in Muffle furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.Inventor uses
D/max-2200X type x ray diffractometer x, the 4294A type of Anjelen Sci. & Tech. Inc's production of Rigaku company production are accurate
The micro confocal laser Raman spectrometer and U.S. Radiant production of impedance analyzer and the production of Reinshaw company, Britain
Ferroelectricity tester carries out characterization test to its structure and performance, and passes through following various calculating correlation performance parameters:
Permittivity εr: εr=4Ct/ (π ε0d)
Nonlinear factor α: α=[log (I2/I1)]/[log(U2/U1)]
γ: γ=1/2 ε of energy storage density0εrEb 2
In formula, C is capacitor, and t is the thickness of potsherd, ε0For permittivity of vacuum (8.85 × 10-12F/m), d is ceramics
The diameter of piece, I1/I2For current density, U1/U2For operating voltage, EbFor disruptive field intensity.The result is shown in Figure 1~4.
As seen from Figure 1, the ceramic material that prepared by comparative example 1 is pure perovskite-like structure, in Examples 1 to 3, in ceramics
After mixing aluminium oxide in material, occurs CuAl in ceramics sample2O4Spinel and TiO2Phase, while with alumina doped amount
Increase, CuAl2O4Spinel and TiO2Phase diffraction peak intensity gradually increases.From Figure 2 it can be seen that ceramic material is presented well
Giant dielectric, very high dielectric constant (> 10 is all kept in 40Hz to 100kHz range3).As seen from Figure 3, comparative example 1
Ceramic material crystal grain with Examples 1 to 3 preparation is in wavelength 265cm-1、443cm-1、510cm-1、575cm-1There are four allusion quotations
The Raman spectral peaks of type, correspond respectively to Fg(1)、Ag(1)、Ag(2) TiO6Rotary mode and Fg(3) the anti-flexible vibration of O-Ti-O
Dynamic model formula.From fig. 4, it can be seen that ceramic material energy storage density prepared by comparative example 1 is about 0.2mJ/cm3, doped Al2O3It is i.e. real afterwards
The ceramic material energy storage density for applying the preparation of example 1~3 is significantly improved, about 0.54~1.52mJ/cm3, especially work as Al2O3It mixes
When miscellaneous amount is 3.0wt%, energy storage density is up to 1.52mJ/cm3.It can be seen that ceramic material of the present invention all has higher storage
Energy density, it is practical, it is expected to the dynamic random storage electronic markets such as (DRAM) and chip multilayer ceramic capacitor (MLCC) and answers
With.
Claims (6)
1. a kind of alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density, it is characterised in that: the ceramic material by
CdCu3Ti4O12-x wt% Al2O3The material of expression forms, whereinxValue be 2~9；The ceramic material is by following methods system
It is standby to obtain:
(1) according to CdCu3Ti4O12Stoichiometric ratio, by Cd (NO3)2•4H2O、Cu(NO3)2•3H2O be added to dehydrated alcohol with
The in the mixed solvent of deionized water is configured to solution A, by Ti (C4H9O)4It is added in dehydrated alcohol and is configured to solution B；By solution
A and solution B mixing, and are added glacial acetic acid, in gained mixed liquor the concentration of butyl titanate be 0.3~0.7mol/L, glacial acetic acid
Volume fraction is 2.5%~10%, the volume fraction of deionized water is 5%~15%, heats and stirs evenly at 30~75 DEG C, obtains
To colloidal sol, continue stirring until colloidal sol becomes gel, drying, obtains xerogel after gel is aged；After xerogel is ground,
It is calcined 8~10 hours at 600~700 DEG C, obtains CdCu3Ti4O12Ceramic powder；
(2) to CdCu3Ti4O12The alumina powder of its quality 3%~12% is added in ceramic powder, through ball milling, drying, granulation, pressure
After piece, dumping, it is sintered 10~15 hours at 970~1000 DEG C, obtains alumina doped copper titanate cadmium giant dielectric ceramic material.
2. the alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density according to claim 1, feature exist
In: it is describedxValue be 2~4.
3. the alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density according to claim 1, feature exist
In: in step (1), the concentration of butyl titanate is 0.5mol/L in gained mixed liquor, the volume fraction of glacial acetic acid is 5%, deionization
The volume fraction of water is 10%.
4. the alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density according to claim 1, feature exist
In: in step (1), heats and stir evenly at 40~50 DEG C, obtain colloidal sol.
5. the alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density according to claim 1, feature exist
In: in step (1), after xerogel is ground, calcined 10 hours at 650 DEG C.
6. the alumina doped copper titanate cadmium giant dielectric ceramic material of high energy storage density according to claim 1, feature exist
In: in step (2), it is sintered 15 hours at 990 DEG C.
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| CN101786876A (en) * | 2009-12-31 | 2010-07-28 | 西北大学 | Barium titanate-based Y5V nano-powder and preparation method for ceramic material thereof |
| CN102701273A (en) * | 2012-05-22 | 2012-10-03 | 山东大学 | Preparation method of nano dysprosium titanate powder |
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| CN101786876A (en) * | 2009-12-31 | 2010-07-28 | 西北大学 | Barium titanate-based Y5V nano-powder and preparation method for ceramic material thereof |
| CN102701273A (en) * | 2012-05-22 | 2012-10-03 | 山东大学 | Preparation method of nano dysprosium titanate powder |
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| "Li0.01Cd0.99Cu3Ti4O12巨介电陶瓷制备及介电性能研究";赵楠等;《第八届中国功能材料及其应用学术会议-摘要》;20130823;权利要求10-12 * |
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